US2633467A - N-hydroxyalkyl-2-ketopiperazines - Google Patents

N-hydroxyalkyl-2-ketopiperazines Download PDF

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Publication number
US2633467A
US2633467A US270770A US27077052A US2633467A US 2633467 A US2633467 A US 2633467A US 270770 A US270770 A US 270770A US 27077052 A US27077052 A US 27077052A US 2633467 A US2633467 A US 2633467A
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ketopiperazine
parts
ketopiperazines
hydroxyalkyl
oxide
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US270770A
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Benneville Peter L De
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Rohm and Haas Co
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Rohm and Haas Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
    • C07D241/08—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms

Definitions

  • This invention relates to new -hydroxyalkyl- Z-ketopiperazines and to a method for their preparation.
  • ketopiperazines of the formula wherein R. is an alkylene group and R and R" have the significance stated above.
  • ketopiperazine there may be used a compound such as 2-ketopiperazine, 3-methyl-2- ketopiperazine, 3,3-dimethyl-2-ketopiperazine, 3- ethyl 2 ketopiperazine, 3 ethyl 3-methyl-2- ketopiperazine, 3-propyl-2-ketopiperazine, 3-butyI-Z-ketopiperazine, and the like.
  • alkylene oxides ethylene oxide and propylene oxide are of primary importance.
  • Other oxlrane compounds can, however, be used, particularly styrene oxide, butadiene monoxide, butylene oxide, and so on.
  • alkylene chain of two carbon atoms attached to oxygen. The chain appears between oxygen and nitrogen in the 4-hydroxyalkyl-2- ketopiperazines which are formed. 4
  • the reaction between a 2-ketopiperazine and an alkylene oxide is carried out by bringing these two materials together at a temperature between 25 and 80 0., preferably in the presence of a solvent such as water or a lower aliphatic monohydric alcohol. In general it is best to add the alkylene oxide to the ketopiperazine under controlled conditions, cooling being supplied as needed. An approximately molar amount of alkylene oxide is desired per mole of ketopiperazine.
  • the reaction mixture may be stirred and heated to complete the reaction.
  • the products can usually be isolated through distillation or crystallization.
  • Example 1 A solution of 57 parts of 3-methyl-2-ketopiperazine, parts of ethylene oxide, and 100 parts of water was carefully heated to C. and maintained at this temperature by cooling. When cooling was no longer needed, the mixture was heated at 50-60 C. for an hour. The reaction mixture was stripped under reduced pressure and distilled. At l-205 C./ 1.5 mm. there was taken a fraction of 34 parts which corresponded in composition to 3-methyl-4-[3-hydroxyethyl-2- ketopiperazine. The distillate contained by analysis 17.3% of nitrogen (theory 17.7%).
  • Example 2 To a solution of 25.6 parts of 3,3-dimethyl-2- ketopiperazine in 50 parts of water there was gradually added ethylene oxide to an amount of 8.8 parts. The reaction was initiated by heating to 40 C. The temperature was allowed to rise to about 50 C. and was held at this level by cooling. Another six parts of ethylene oxide was run in. When the temperature fell, the reaction mixture was distilled. At 210-240 C./22 mm. a fraction of 27 parts of a thick yellow oil was obtained. This solidified when cool. The solid was recrystallized from isopropanol and ethyl acetate. The product then melted at -108 C. It corresponded in composition to 3,3-dimethy1-4-13-hydroxyethyl-2-ketopiperazine. It contained by analysis 16.2% of nitrogen (theory 16.3%).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

Patented Mar. 31, 1953 UNITED STATES TENT OFFICE N -HYDROXYADKYL- 2 -KETOPIPERAZINE S Peter L. de Benneville, Philadelphia, Pa, assi'g'nor to Rohm & Haas Company, Philadelphia, Pa
a corporation of Delaware.
No Drawing. Application February 8, 1952, Serial No. 270,770
3 Claims.
This invention relates to new -hydroxyalkyl- Z-ketopiperazines and to a method for their preparation.
It has been found that ketopiperazines of the formula wherein R. is an alkylene group and R and R" have the significance stated above.
These products are of interest because they contain a reactive amido linkage and. an alcoholic hydroxyl group in addition to a tertiary amine group. They are of value in the preparation and modification of resins. They provide compounds having therapeutic action. Some of the new compounds have fungicidal and pesticidal properties.
As a ketopiperazine there may be used a compound such as 2-ketopiperazine, 3-methyl-2- ketopiperazine, 3,3-dimethyl-2-ketopiperazine, 3- ethyl 2 ketopiperazine, 3 ethyl 3-methyl-2- ketopiperazine, 3-propyl-2-ketopiperazine, 3-butyI-Z-ketopiperazine, and the like.
As alkylene oxides, ethylene oxide and propylene oxide are of primary importance. Other oxlrane compounds can, however, be used, particularly styrene oxide, butadiene monoxide, butylene oxide, and so on. In these compounds there is an alkylene chain of two carbon atoms attached to oxygen. The chain appears between oxygen and nitrogen in the 4-hydroxyalkyl-2- ketopiperazines which are formed. 4
The reaction between a 2-ketopiperazine and an alkylene oxide is carried out by bringing these two materials together at a temperature between 25 and 80 0., preferably in the presence of a solvent such as water or a lower aliphatic monohydric alcohol. In general it is best to add the alkylene oxide to the ketopiperazine under controlled conditions, cooling being supplied as needed. An approximately molar amount of alkylene oxide is desired per mole of ketopiperazine. The reaction mixture may be stirred and heated to complete the reaction. The products can usually be isolated through distillation or crystallization.
The following example illustrate this invention and supply additional details of procedure. Parts are by weight.
Example 1 A solution of 57 parts of 3-methyl-2-ketopiperazine, parts of ethylene oxide, and 100 parts of water was carefully heated to C. and maintained at this temperature by cooling. When cooling was no longer needed, the mixture was heated at 50-60 C. for an hour. The reaction mixture was stripped under reduced pressure and distilled. At l-205 C./ 1.5 mm. there was taken a fraction of 34 parts which corresponded in composition to 3-methyl-4-[3-hydroxyethyl-2- ketopiperazine. The distillate contained by analysis 17.3% of nitrogen (theory 17.7%).
Example 2 To a solution of 25.6 parts of 3,3-dimethyl-2- ketopiperazine in 50 parts of water there was gradually added ethylene oxide to an amount of 8.8 parts. The reaction was initiated by heating to 40 C. The temperature was allowed to rise to about 50 C. and was held at this level by cooling. Another six parts of ethylene oxide was run in. When the temperature fell, the reaction mixture was distilled. At 210-240 C./22 mm. a fraction of 27 parts of a thick yellow oil was obtained. This solidified when cool. The solid was recrystallized from isopropanol and ethyl acetate. The product then melted at -108 C. It corresponded in composition to 3,3-dimethy1-4-13-hydroxyethyl-2-ketopiperazine. It contained by analysis 16.2% of nitrogen (theory 16.3%).
Example 3 3 '4 I claim: 2. As a. new chemical compound, 3-methyi-4- 1. As new chemical substances, compounds of fi-hydroxyethyl-Z-ketopiperazine. the formula 3. As a new chemical compound, 3,3-dimethy1- ROE -p-hydroxyethyl-2-ketopiperazine. 1 R, 5 PETER L. on BENNEVELE. 0Q, o REFERENCES CITED l B The following references areof record in the H2 C: file of this patent: Aspinali: J. Am. Chem. 800., 62, pp. 1202-1204 wherein R is an alkyiene group having a. chain of two carbon atoms between oxygen and nitrogen and R and R" represent members of the class consisting of hydrogen and alkyl groups of one to 15 four carbon atoms.
Kitchen 815 9.1.: J. Org. Chem, 8, 337-340 (1942).

Claims (1)

1. AS NEW CHEMICAL SUBSTANCES, COMPOUND OF THE FORMULA
US270770A 1952-02-08 1952-02-08 N-hydroxyalkyl-2-ketopiperazines Expired - Lifetime US2633467A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2925420A (en) * 1957-09-25 1960-02-16 Abbott Lab Piperazine derivatives
US3146234A (en) * 1959-09-25 1964-08-25 Sterling Drug Inc 1-substituted-2-piperazinones and 1-substituted-7-homopiperazinones
US4190571A (en) * 1977-09-21 1980-02-26 The B. F. Goodrich Company Substituted 2-keto-1,4-diazacycloalkanes and UV-light-stabilized compositions containing them
US4980471A (en) * 1989-10-06 1990-12-25 The Dow Chemical Company Preparation of piperazinones for use as sulfur dioxide absorbents

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2925420A (en) * 1957-09-25 1960-02-16 Abbott Lab Piperazine derivatives
US3146234A (en) * 1959-09-25 1964-08-25 Sterling Drug Inc 1-substituted-2-piperazinones and 1-substituted-7-homopiperazinones
US3188313A (en) * 1959-09-25 1965-06-08 Sterling Drug Inc 1-[(1-, 2- and 3-indolyl)-lower]piperazine derivatives and intermediates and processes for the preparation thereof
US4190571A (en) * 1977-09-21 1980-02-26 The B. F. Goodrich Company Substituted 2-keto-1,4-diazacycloalkanes and UV-light-stabilized compositions containing them
US4980471A (en) * 1989-10-06 1990-12-25 The Dow Chemical Company Preparation of piperazinones for use as sulfur dioxide absorbents

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